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Патент USA US2119882

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Patented June 7, 1938
2,119,882
UNITED STATES
PATENT OFFICE
2,119,882
ALIINOTRIFLUOROMETHYLeARYL- SUL
PHONIC ACIDS AND PROCESS OF PRE
PARING THEM
Herbert Kracker and Fritz Herrlein, Frank
fort-on-the-Main-Hochst, Germany, as
signors to General Aniline Works, Inc.,
New York, N. Y., a corporation of Dela
ware
N0 Drawing.
Application September 27,
1935, Serial No. 42,512. In Germany 00
tober 3, 1934
7 Claims.
This invention relates to aminotrifiuoromethyl
aryl-sulphonic acids and to a process vof preparing
them; more particularly it relates to compounds
corresponding with the following general formula
'
5
NHg
(Cl. 260-129)
the base to react in an inert organic solvent at a
raised temperature.
'
This reaction is the more surprising since,
generally, the action of chlorosulphonic acid on
tri?uoromethyl-compounds takes another course.
By introducing, for instance, benzotri?uoride in
to an excess of chlorosulphonic acid and allow
ing the whole to stand for some time, an ex
change between the tri?uoromethyl group and
10
the chlorosulphonic acid occurs in such a man
SOaH
wherein the benzene nucleus may be further sub
stituted by halogen, alkoxy, phenoxy, benzyloxy,
nitro, trifluoromethyl, alkylsulphonyl, phenyl
sulphonyl or benzylsulphonyl groups.
Sulphonic acids of aminotri?uoromethyl
aryls have not yet been described in literature.
Attempts to make these unknown sulphonic acids
20
by sulphonating aminotri?uoromethyl-aryls, for
?uoromethyl compounds the tri?uoromethyl
instance, by means of concentrated sulphuric
acid, sulphuric acid monohydrate or fuming sul
phuric acid, at ordinary or raised temperature.
group would be destroyed in a similar way. The 20
new sulphonic acids may be used as interme
diates for the manufacture of dyestuffs. '
show that sulphonation does not occur. The
25 tri?uoromethyl group is saponi?ed to form the
carboxylic acid group or the amine remains com
The following examples illustrate the inven
tion.
1. 161 grams of 1-amino-3-trifluoro-methyl
pletely unchanged, and only the sulphate of the
benzene are dissolved in 1000 cc. of orth'o-dichlo
base is formed. The ?rst reaction occurs when
sulphuric acid or sulphuric acid monohydrate is
robenzene which has been carefully dried.
While well stirring, 120 grams of freshly distilled
chlorosulphonic acid are added by drops. The
whole is then slowly heated to boiling at about
180 G. Rapid evolution of hydrochloric acid
30 used at raised temperature.
By treating, for in
tance, meta-aminobenzotri?uoride at 100° C. or
a higher temperature with sulphuric acid of 97
per cent. strength or sulphuric acid monohy
drate, then pouring on ice and working up the
35
10
ner that benzotrichloride and ?uorosulphonic
acid are formed; by pouring the mixture into
water, the benzotrichloride is saponi?ed with
formation of benzoic acid. Thus, it is not pos
sible to obtain in this manner sulphonic acid 15
derivatives of tri?uoromethyl bodies. In view
of this fact, it was expected that by the action
of chlorosulphonic acid on amino-substituted tri
mixture, there is obtained meta-amino-benzoic
acid. At a lower temperature or by using fuming
sulphuric acid of 10-70 per cent, strength at any
temperature and working up by pouring the mix
ture on ice, there is obtained the sulphate of the
By conducting the reaction with molecu
lar proportions of sulphuric acid, sulphuric acid
40 base.
monohydrate or fuming sulphuric acid in an or
ganic solvent, for instance, in ortho-dichloro
gas sets in. After about 4-5 hours the evolution
of hydrochloric acid has ceased. The Whole is
allowed to cool, the body which is suspended in
the ortho-dichlorobenzene is ?ltered by suction, 35
washed with ether and dried. The dry powder
is dissolved in 600 cc. of warm 2N-sodium carbon
ate solution and 1000 cc. of water, freed from
any separated unsulphonated base by extraction
with ether and rendered acid to Congo‘ paper by 40
means of hydrochloric acid. The 1-amino-3-tri
?uoromethylbenzene-li-sulphonic acid produced
This invention relates to a process in which
chlorosulphonic acid is used as a sulphonating
is thus precipitated in the form of very ?ne small
white needles which are ?ltered by suction,
washed with water and dried. The compound
forms in the dry state a loose white powder.
agent, whereby the formation of the sulphonic
It corresponds with the following formula: '
benzene at l'70°—180° 0., there is obtained in most
45 cases the sulphate of the base in question.
acids desired occurs in a smooth course.
The re
50 action with chlorosulphonic acid may be per
formed, for instance, by introducing the base to
be sulphonated into an excess of chlorosulphonic
acid and by carrying out the sulphonation at or
dinary or raised temperature, or by causing mo
55 lecular proportions of chlorosulphonic acid and
2,119,882
2
By Working in a similar manner with l-amino
4 - trifluoromethylbenzene,
1-amino-4-tri?uoro
methylbenzene-Z-sulphonic acid is obtained.
1
amino 4 2 - tri?uoromethylbenzene - 4 - sulphonic
acid is obtained in a similar manner from l-am
ino-2-trifluoromethylbenzene. Both acids are
likewise obtained in the form of a white powder.
2. 196 grams of 1-amino-21-chlor0-5-tri?uoro
methylbenzene are dropped into 1000 grams of
10 chlorosulphonic acid, while cooling with ice. A
clear solution is obtained. The whole is stirred
for 24 hours and the mixture is cautiously poured
on ice. The separated body is ?ltered by suc
tion, washed and dissolved in sodium carbonate
solution and water as described in Example 1.
By acidifying with hydrochloric acid, 1-amino-2
chloro- 5 -trifluoromethylbenzene- 4 -sulphonic
acid is obtained in the form of ?ne small white
needles. The same sulphonic acid is obtained by
20 conducting the sulphonation, as described in Ex
ample 1, in chlorobenzene at 110° C.
In the same manner there are obtained 1-am
inc-2,4-dichloro-5-tri?uorometthylbenzenie-6-sufl
phonic acid from 1-amino-2,4-dichloro-5-tri
fluoro-methylbenzene,
1-amino-2,5-dichloro-3
tri?uoromethylbenzene-4-sulphonic acid from 1
amino - 2,5 - dichloro- 3 -tri?uoromethylbenzene,
and 1-amino-2-bromo-5-tri?uoromethylbenzene
4-sulphonic acid from 1-amino-2-bromo-5-tri
fluoromethylbenzene.
3. 196 grams of l-amino-4-chloro-2-trifluoro
methylbenzene are sulphonated in 1000 cc.
of chlorobenzene as described in Example 1 at
110°-120° C. After about 2 hours the evolution
of hydrochloric acid gas is ?nished. After work
ing up as described in Example 1, 1-amino-4
chloro - 2-trifluoromethylbenzene - G-sulphonic
acid is obtained in the form of a white micro
6. 206 grams of 1-amino-2-nitro-4-tri?uoro
methylbenzene are disolved in 1000 cc. of nitro
benzene and 120 grams of chlorosulphonic acid
are then run in.
In the manner described in
Example 1, the sulphonation is performed at 110°
C. The sulphonic acid is ?ltered by suction,
washed with ether and dried. The acid thus iso
lated is a yellow powder which in the form of 10
the free acid as well as in that of the sodium salt
is very easily soluble in water. By adding so
dium chloride to the alkaline solution, the so
dium salt of 1-amino-2-nitro~4-trifluoromethyl
benzene-G-sulphonic acid is obtained in the form
of yellow loose crystalline needles.
By adding
sodium chloride to the solution of the free sul
phonic acid in water, the free sulphonic acid is
obtained in the form of a loose yellow crystalline
powder.
.
In a similar manner 1-amino-2-nitro-5-tri
fluoro-methylbenzene-4-sulphonic acid is ob
tained from l-amino-Z-nitro-5-tri?uoromethyl
benzene and 1-amino-4-nitro~5-trifluoromethyl
benzene-Z-sulphonic acid from 1-amino-4-nitr0
5-tri?uoromethylbenzene.
'7. In the manner described in the foregoing
examples, 230 grams of 1-amino-3,5-bis-trifluoro—
methylbenzene are sulphcnated in 1000 cc. of
tetrachlorethane with 120 grams of chlorosul
phonic acid at 130° C. This acid, too, as well as
its sodium salt, is very easily soluble in water and,
when redissolved, they must be isolated by addi—'
tion of a salt. 1-amino-3,5-bis-tri?uoromethyl
benzene-ll-sulphonic acid is thus obtained in the 35
form of ?ne White crystals; the sodium salt forms
similar crystals.
In the same manner there are obtained l-am
ino-2,5-bis—tri-?uoromethylbenzene-4 - sulphonic
crystalline powder.
acid from 1-amino-2,5-bis-tri?uoromethylben—
4. 196 grams of 1-amino-4-chloro-3-trifluoro
methylbenzene are caused to react at about
160° C. with 120 grams of chlorosulphonic acid in
1000 ‘cc. of a technical mixture consisting of
methylbenzene~4-sulphonic acid from 1-amino-2
ortho-dichlorobenzene and para-dichlorobenzene,
in the manner described in Example 1. The sul
phonation is ?nished after 2—3 hours. After
working up as usual, 1-amino-4-chloro-3-tri
?uoromethylbenzene-6-sulphonic acid is obtained
in the form of a white micro-crystalline powder.
5. 191 grams of ?nely powdered l-amino
2-methoxy-S-tri?uoromethylbenzene are intro
duced into 1000 grams of chlorosulphonic acid.
The whole is stirred, until a clear solution is ob
tained and heated slowly to 120° C. After 4-5
hours the sulphonation is ?nished. The whole
is poured on ice with precaution, the precipitate
formed is ?ltered with suction and dissolved in
warm sodium carbonate solution and water. Any
(if)
phonic acid from 1-amino-2..4-dimethoxy-B-tri
fluoromethylbenzene.
base which might be present is extracted with
ether. On acidi?cation, 1-amino-2-methoxy-5
tri?uoro-methylbenzene-4-sulphonic acid is ob
tained in the form of needles.
zene
and
1-amino-2-chloro—3,5-bis-trifluoro
chloro-3,5-bis-trifluoromethylbenzene.
8. 251 grams of 1-amino-5—trifluoromethylben~
zene-2-ethylsulphone are dissolved in 1000 cc. of
ortho-dichlorobenzene and 120 grams of freshly
distilled chlorosulphonic acid are added by drops.
The whole is then slowly heated to 120° C. and
this temperture is maintained until the evolution
of hydrochloric acid gas decreases. Thereupon,
further 120 grams of chlorosulphonic acid are
added, heating is continued at 120° C., until the
I
evolution of hydrochloric acid decreases, there
upon a further 240 grams of chlorosulphonic acid
are added. As soon as, after this last addition, 55
hydrochloric acid gas is evolved only feebly at a
temperature of 120° C., the whole is allowed to
cool. The separated product is ?ltered with suc
tion, washed with ether and dried. It is dissolved
in 600 cc. of 2N-sodium carbonate solution, the
free base which might be present is removed by
extraction with ether, and the double quantity
by volume of saturated sodium chloride solution
In a similar manner there are obtained l-am
ino-4-methoxy-5—trifluoromethylbenzene-2 - sul
is added to the clear aqueous solution.
phonic acid from 1-arnino-4-methoxy—5—tri?uoro
2-ethylsulphone-4-sulphonic acid thus produced
methylbenzene, l-arnino-~2v - ethoxy-5 - tri?uoro
crystallizes in the form of white small needles
which are separated from the mother liquor by
?ltering with suction and washed with saturated
70
sodium chloride solution until neutral.
methylbenzene-4-sulphonic acid from l-amino
2-ethoxy-5-trifluoromethylbenzene,
1-amino-4
70 phenoxy-5-tri?uoromethylbenzene - 2 - sulphonic
The so
dium salt of 1-amino-5-trifluoromethylbenzene
acid from 1-amino-4-phenoxy—5—tri?uorometh
In a similar manner there are obtained 1
lybenzene, 1-amino-2-benzyloxy-5-trifluorometh
amino-3 - tri?uoromethylbenzene - 4 - methylsul
ylbenzene-ll-sulphonic acid from
1-amino-2
phone-G-sulphonic acid from 1-amino-3-tri?u
benzyloxy-5-triiluoromethylbenzene,
l-amino
2.4-dimethoxy-5-tri?uoromethylbenzene - 6 - sul
oromethylbenzene - 4 - methylsulphone, l-amino
2-tri?uoromethylbenzene - 4 - phenylsulphone -6;.
75
2,119,882
sulphonic acid from 1-amino-2-trifluoromethyl
benzene-‘l-phenylsulphone and l-amino-5-triflu
oromethylbenzene-2—benzylsulphone-4- sulphonic
acid from 1-amino-5-tri?uoromethylbenzene-2
benzylsulphone.
Besides the indifferent organic solvents men\
tioned in the foregoing examples there may be
used other solvents, for instance other halogen
substitution products of the aromatic or aliphatic
3
consisting of hydrogen, halogen, alkoxy, phenoxy,
benzyloxy, nitro and tri?uoromethyl and Y stands
for a member of the group consisting of hydro
gen, halogen and alkoxy, being crystallized com
pounds which are easily soluble in aqueous alka
lies and insoluble in organic solvents.
5__. The compound of the following formula:
are
series, such as trichlorobenzene, chlorxylenes,
1O
halogenated ethanes or the like. By using any
other amine of the tri?uoromethyl series the
CF:
sulphonation occurs in the same.manner as in
the foregoing examples.
15
We claim:
1. The process of preparing aminotri?uoro
methyl-benzene-sulphonic acids which comprises
causing a molecular excess of chlorosulphonic
acid to act upon aminotri?uoromethyl~benzenes
20 at temperatures up to about 180° C.
2. The process of preparing aminotri?uoro
methyl-benzene-sulphonic acids which comprises
causing chlorosulphonic acid and aminotri?uoro
methyl-benzenes to react in an inert organic sol
vent at temperatures of about 110° C. to about
180° C.
3. The process of preparing aminotri?uoro
methyl-benzene-sulphonic acids which comprises
causing molecular proportions of chlorosulphonic
30 acid and aminotri?uoromethyl—benzenes to react
in an inert organic solvent at temperatures of.
about 110° C. to about 180° C.
4. The compounds of the following general for
mula
SORH
being easily soluble in aqueous alkalies and dim
cultly soluble in water from which it crystallizes
in the form of ?ne small white needles.
6. The compound of the following formula:
NH:
—Cl
FaC
SOaH
being easily soluble in aqueous alkalies and diffi
cultly soluble in water from which it crystallizes
in the form of ?ne small white needles.
'7. The compound of the following formula:
rm
Hms
—No,
NH:
Y I
CO on
F:
40
86,11
wherein X stands for a member of the group
30
being a loose yellow crystalline powder which is
easily soluble in water and aqueous alkalies.
HERBERT KRACKER.
FRITZ HERRLEIN.
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